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journal article·2021-10Open access

Identification of Topotactic Surface‐Confined Ullmann‐Polymerization

Dominik Dettmann, Gianluca Galeotti, Oliver MacLean, Massimo Tomellini, Marco Di Giovannantonio, Josh Lipton‐Duffin, Alberto Verdini, Luca Floreano, Yannick Fagot‐Revurat, Dmitrii F. Perepichka, Federico Rosei, Giorgio Contini

Small· Volume 17· Issue 41
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Source abstract

Abstract

Abstract On‐surface Ullmann coupling is an established method for the synthesis of 1D and 2D organic structures. A key limitation to obtaining ordered polymers is the uncertainty in the final structure for coupling via random diffusion of reactants over the substrate, which leads to polymorphism and defects. Here, a topotactic polymerization on Cu(110) in a series of differently‐halogenated para‐phenylenes is identified, where the self‐assembled organometallic (OM) reactants of diiodobenzene couple directly into a single, deterministic product, whereas the other precursors follow a diffusion driven reaction. The topotactic mechanism is the result of the structure of the iodine on Cu(110), which controls the orientation of the OM reactants and intermediates to be the same as the final polymer chains. Temperature‐programmed X‐ray photoelectron spectroscopy and kinetic modeling reflect the differences in the polymerization regimes, and the effects of the OM chain alignments and halogens are disentangled by Nudged Elastic Band calculations. It is found that the repulsion or attraction between chains and halogens drive the polymerization to be either diffusive or topotactic. These results provide detailed insights into on‐surface reaction mechanisms and prove the possibility of harnessing topotactic reactions in surface‐confined Ullmann polymerization.
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Research context

Polymers

OpenAlex topics: Surface Chemistry and Catalysis · Photonic Crystals and Applications · Block Copolymer Self-Assembly

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Centre Énergie Matériaux et Télécommunications Institut National de la Recherche Scientifique Department 1650 Boulevard Lionel‐Boulet, J3X1S2 Varennes Québec Canada

Istituto di Struttura della Materia Consiglio Nazionale delle Ricerche Via Fosso del Cavaliere 100 Roma 00133 Italy

Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education Jilin Normal University Changchun 130103 P. R. China

Department of Chemistry University Tor Vergata Via della Ricerca Scientifica 1 Roma 00133 Italy

School of Chemistry and Physics Queensland University of Technology 2 George Street Brisbane 4001 QLD Australia

Istituto Officina dei Materiali Consiglio Nazionale delle Ricerche S.S. 14, km 163.5 Trieste I‐34149 Italy

Institut Jean Lamour Campus ARTEM UMR 7198 CNRS‐Université de Lorraine 2 allée André Guinier BP 50840 Nancy 54011 France

Department of Chemistry McGill University 801 Sherbrooke Street West Montreal QC H3A 0B8 Canada

Department of Physics University Tor Vergata Via della Ricerca Scientifica 1 Roma 00133 Italy

Funding

Ministero degli Affari Esteri e della Cooperazione Internazionale

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